Method for the continuous production of biodegradable polyesters

ABSTRACT

A process for the continuous production of a biodegradable polyester, where 
     a mixture of aliphatic dihydroxy compounds, aliphatic and aromatic dicarboxylic acids or their liquid esters, and, optionally, further comonomers is mixed, without addition of a catalyst, to give a paste, and 
     
         
         
           
             i) this mixture with at least a portion of the catalyst, is continuously esterified or, transesterified; 
             ii) the transesterification or, esterification product obtained in i) is continuously precondensed with any remaining amount of catalyst to an intrinsic viscosity of from 20 to 70 cm 3 /g; 
             iii) the product obtainable from ii) is continuously polycondensed to an intrinsic viscosity of from 60 to 170 cm 3 /g, and 
             iv) the product obtainable from iii) is reacted continuously with a chain extender in a polyaddition reaction to an intrinsic viscosity of from 150 to 320 cm 3 /g. 
           
         
       
    
     The invention further relates to biodegradable polyesters obtained_by this process.

CROSS REFERENCE TO RELATED APPLICATIONS

This Application is a Division of application Ser. No. 12/988,127, filedon Oct. 15, 2010, which is a national stage application under 35 U.S.C.§371 of PCT/EP2009/054116, filed Apr. 7, 2009, which claims benefit toEuropean application 08154541.0, filed Apr. 15, 2008, the entiredisclosures of which are hereby incorporated by reference.

The present invention relates to a process for the continuous productionof a biodegradable polyester based on aliphatic or aliphatic andaromatic dicarboxylic acids and on aliphatic dihydroxy compounds, where

a mixture composed of the aliphatic dihydroxy compounds, of thealiphatic and aromatic dicarboxylic acids, and, if appropriate, offurther comonomers (component C) is mixed, without addition of acatalyst, to give a paste, or, as an alternative, the liquid esters ofthe dicarboxylic acids are fed into the system, as also are thedihydroxy compound and, if appropriate, further comonomers, withoutaddition of any catalyst, and

-   -   i) in a first stage, this mixture, together with the entire        amount or with a portion of the catalyst, is continuously        esterified or, respectively, transesterified;    -   ii) in a second stage, the transesterification or, respectively,        esterification product obtained in i) is continuously        precondensed if appropriate with the remaining amount of        catalyst to an intrinsic viscosity of from 20 to 70 cm³/g to DIN        53728;    -   iii) in a third stage, the product obtainable from ii) is        continuously polycondensed to an intrinsic viscosity of from 60        to 170 cm³/g to DIN 53728, and    -   iv) in a fourth stage, the product obtainable from iii) is        reacted continuously with a chain extender D in a polyaddition        reaction to an intrinsic viscosity of from 150 to 320 cm³/g to        DIN 53728.

In particular, the invention relates to a process for the continuouspreparation of a biodegradable polyester based on aliphatic and aromaticdicarboxylic acids and on aliphatic dihydroxy compounds, where

a mixture composed of the aliphatic dihydroxy compounds, of thealiphatic and aromatic dicarboxylic acids, and, if appropriate, offurther comonomers (component C) is mixed, without addition of acatalyst, to give a paste, or, as an alternative, the liquid esters ofthe dicarboxylic acids are fed into the system, as also are thedihydroxy compound and, if appropriate, further comonomers, withoutaddition of any catalyst, and

-   -   i) in a first stage, this mixture, together with the entire        amount or with a portion of the catalyst, is continuously        esterified or, respectively, transesterified;    -   ii) in a second stage, the transesterification or, respectively,        esterification product obtained in i) is continuously        precondensed if appropriate with the remaining amount of        catalyst to an intrinsic viscosity of from 20 to 60 cm³/g to DIN        53728;    -   iii) in a third stage, the product obtainable from ii) is        continuously polycondensed to an intrinsic viscosity of from 70        to 130 cm³/g to DIN 53728, and    -   iv) in a fourth stage, the product obtainable from iii) is        reacted continuously with a chain extender D in a polyaddition        reaction to an intrinsic viscosity of from 160 to 250 cm³/g to        DIN 53728.

The invention further relates to biodegradable polyesters which areaccessible for the first time by this process.

The prior art for the production of biodegradable polyesters based onaliphatic and aromatic dicarboxylic acids and on aliphatic dihydroxycompounds in particular describes batch processes (WO-A 92/09654 andWO-A 96/15173). A disadvantage of these is that the aliphatic/aromaticpolyesters require a relatively long residence time in the reactionvessel at high temperatures in order to reach high molecular weight—thedesired intrinsic viscosity being greater than 160 cm³/g to DIN 53728. Aresult of the long residence times at high temperatures is a certainamount of degradation of the sensitive aliphatic/aromatic polyesters.The acid number of the polyesters rises rapidly and can easily reachvalues greater than 1.6 mg KOH/g. High acid numbers cause problemsduring the subsequent chain-extension process (particularly usingisocyanates). It then becomes impossible to achieve higher molecularweights. Materials of this type achieve only low viscosities, and oftenhave fish eyes and cannot then be used for numerous injection-molding orextrusion applications. Finally, biodegradable polyesters with high acidnumber have very limited hydrolysis resistance.

The literature describes efficient, continuous processes for theproduction of aromatic polyesters, such as PET and PBT (see, forexample, WO 03/042278 and DE-A 199 29 790). However, these cannot bedirectly transferred to aliphatic/aromatic polyesters. Firstly, thearomatic polyesters often have relatively high acid numbers, andsecondly the problem of hydrolysis resistance is less severe in aromaticpolyesters than in aliphatic/aromatic polyesters.

It was an object of the present invention, accordingly, to provide anindustrial process which permits the production of biodegradablealiphatic or aliphatic/aromatic (semiaromatic) polyesters with intrinsicviscosities to DIN 53728 of from 150 to 320 and acid numbers to DIN EN12634 smaller than 1.2 mg KOH/g, preferably smaller than 1.0 mg KOH/g.Other factors of great importance for an industrial process areprocessability and cost-effectiveness (product yield and space/timeyield).

Surprisingly, the continuous, 4-stage process mentioned in theintroduction achieves every aspect of the object.

One preferred embodiment of the process of the invention (see claims 6,17, 18) moreover for the first time permits provision of biodegradablesemiaromatic polyesters with intrinsic viscosities greater than 160cm³/g and acid numbers smaller than 1.0 mg KOH/g, and with MVR smallerthan 6.0 cm³/10 min (measured at 190° C., with a weight of 216 kg) (seeclaim 19). These are substantially more resistant to hydrolysis than thebiodegradable polyesters described for example in WO-A 96/15173. Thepolyesters are therefore easier to process. This moreover providesaccess to new application sectors including those in mixtures with otherbiopolymers that are susceptible to hydrolysis, examples being PLA(polylactide); PHA (polyhydroxyalkanoates), PBS (polybutylenesuccinate), and starch.

Biodegradable polyesters are aliphatic and semiaromatic polyesters—asdescribed by way of example in WO-A 96/15173 and DE-A 10 2005053068.

In particular, biodegradable polyesters are aliphatic/aromaticpolyesters whose structure is as follows:

-   A) an acid component composed of    -   a1) from 30 to 99 mol % of at least one aliphatic dicarboxylic        acid or its esters, or a mixture thereof,    -   a2) from 1 to 70 mol % of at least one aromatic dicarboxylic        acid or its esters, or a mixture thereof, and    -   a3) from 0 to 5 mol % of a compound comprising sulfonate groups,    -   where the total of the molar percentages of components a1) to        a3) is 100%, and-   B) a diol component composed of:    -   b1) at least equimolar amounts with respect to component A of a        C₂-C₁₂ alkanediol, or a mixture thereof, and    -   b2) from 0 to 2% by weight, based on the amount of polyester        after stage iii (which corresponds to the amount used of        components A and B minus the reaction vapors removed), of a        compound comprising at least 3 functional groups;    -   and, if appropriate, one or more components selected from-   C) a component selected from    -   c1) at least one dihydroxy compound comprising ether functions        and having the formula I        HO—[CH₂)_(n)—O]_(m)—H  (I)        -   where n is 2, 3 or 4 and m is a whole number from 2 to 250,    -   c2) at least one hydroxycarboxylic acid of the formula IIa or        IIb

-   -   -   where p is a whole number from 1 to 1500 and r is a whole            number from 1 to 4, and G is a radical selected from the            group consisting of phenylene, —(CH₂)_(q)—, where q is a            whole number from 1 to 5, —C(R)H— and —C(R)HCH₂, where R is            methyl or ethyl,

    -   c3) at least one amino-C₂-C₁₂ alkanol, or at least one        amino-C₅-C₁₀ cycloalkanol, or a mixture of these,

    -   c4) at least one diamino-C₁-C₈ alkane,

    -   c5) at least one aminocarboxylic acid compound selected from the        group consisting of caprolactam, 1,6-aminocaproic acid,        laurolactam, 1,12-aminolauric acid, and 1,11-aminoundecanoic        acid,        -   or mixtures composed of c1) bis c5),        -   and

-   D) from 0.01 to 4% by weight, based on the amount of polyester after    stage iii, of at least one component selected from the group d1) to    d4)    -   d1) of a di- or oligofunctional isoscyanate and/or isocyanurate,    -   d2) of a di- or oligofunctional peroxide,    -   d3) of a di- or oligofunctional epoxide,    -   d4) of a di- or oligofunctional oxazoline, oxazine, caprolactam,        and/or carbodiimide;

-   E) from 0 to 10% by weight, based on the amount of polyester after    stage iii of a component selected from the group e1) to e3)    -   e1) of a lubricant, such as erucamide or a stearate,    -   e2) of a nucleating agent, such as calcium carbonate,        polyethylene terephthalate, or polybutylene terephthalate,    -   e3) of an aliphatic polyester selected from the group consisting        of: polylactic acid, polycaprolactone, polyhydroxyalkanoate.

In one preferred embodiment, the acid component A of the semiaromaticpolyesters comprises from 30 to 70 mol %, in particular from 40 to 60mol %, of a1 and from 30 to 70 mol %, in particular from 40 to 60 mol %,of a2. In one particularly preferred embodiment, the acid component A ofthe semiaromatic polyesters comprises more than 50 mol % of aliphaticdicarboxylic acid a1). A feature of these polyesters is excellentbiodegradability.

Aliphatic acids and the corresponding derivatives a1 which may be usedare generally those having from 2 to 40 carbon atoms, preferably from 4to 14 carbon atoms. They may be either linear or branched. Thecycloaliphatic dicarboxylic acids which may be used for the purposes ofthe present invention are generally those having from 7 to 10 carbonatoms and in particular those having 8 carbon atoms. In principle,however, it is also possible to use dicarboxylic acids having a largernumber of carbon atoms, for example having up to 30 carbon atoms.

Examples which may be mentioned are: malonic acid, succinic acid,glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipicacid, pimelic acid, suberic acid, azelaic acid, sebacic acid,undecanedioic acid, dodecanedioic acid, brassylic acid, tetradecanedioicacid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, dimer fattyacid (e.g. Empol® 1061 from Cognis), 1,3-cyclopentanedicarboxylic acid,1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid,diglycolic acid, itaconic acid, maleic acid, maleic anhydride, and2,5-norbornanedicarboxylic acid.

Ester-forming derivatives of the abovementioned aliphatic orcycloaliphatic dicarboxylic acids which may also be used and which maybe mentioned are in particular the di-C₁-C₆-alkylesters, such asdimethyl, diethyl, di-n-propyl, diisopropyl, di-n-butyl, diisobutyl,di-tert-butyl, di-n-pentyl, diisopentyl or di-n-hexylesters. It is alsopossible to use anhydrides of the dicarboxylic acids.

The dicarboxylic acids or their ester-forming derivatives may be usedhere individually or in the form of a mixture composed of two or more ofthese.

It is preferable to use succinic acid, adipic acid, azelaic acid,sebacic acid, brassylic acid, or their respective ester-formingderivatives, or a mixture thereof. It is particularly preferable to usesuccinic acid, adipic acid, or sebacic acid, or their respectiveester-forming derivatives, or a mixture thereof. It is particularlypreferable to use adipic acid or its ester-forming derivatives, forexample its alkyl esters or a mixture of these. Sebacic acid or amixture of sebacic acid with adipic acid is preferably used as aliphaticdicarboxylic acid when polymer mixtures having “hard” or “brittle”components ii), such as polyhydroxybutyrate or in particularpolylactide, are produced. Succinic acid or a mixture of succinic acidwith adipic acid is preferably used as aliphatic dicarboxylic acid whenproducing polymer mixtures with “soft” or “tough” components ii),examples being polyhydroxybutyrate-co-valerate orpoly-3-hydroxybutyrate-co-4-hydroxybutyrate.

Succinic acid, azelaic acid, sebacic acid, and brassylic acid have theadditional advantage of being available in the form of renewable rawmaterials.

Aromatic dicarboxylic acids a2 which may be mentioned are generallythose having from 8 to 12 carbon atoms and preferably those having 8carbon atoms. By way of example, mention may be made of terephthalicacid, isophthalic acid, 2,6-naphthoic acid and 1,5-naphthoic acid, andalso ester-forming derivatives of these. Particular mention may be madehere of the di-C₁-C₆-alkylesters, e.g. dimethyl, diethyl, di-n-propyl,diisopropyl, di-n-butyl, diisobutyl, di-tert-butyl, di-n-pentyl,diisopentyl; or di-n-hexylesters. The anhydrides of the dicarboxylicacids a2 are also suitable ester-forming derivatives.

However, in principle it is also possible to use aromatic dicarboxylicacids a2 having a greater number of carbon atoms, for example up to 20carbon atoms.

The aromatic dicarboxylic acids or ester-forming derivatives of these a2may be used individually or as a mixture of two or more of these. It isparticularly preferable to use terephthalic acid or its ester-formingderivatives, such as dimethyl terephthalate.

The compound used comprising sulfonate groups is usually one of thealkali metal or alkaline earth metal salts of a dicarboxylic acidcomprising sulfonate groups or ester-forming derivatives thereof,preferably alkali metal salts of 5-sulfoisophthalic acid or a mixture ofthese, particularly preferably the sodium salt.

According to one of the preferred embodiments, the acid component Acomprises from 40 to 60 mol % of a1, from 40 to 60 mol % of a2, and from0 to 2 mol % of a3.

The dials B are generally selected from branched or linear alkanediolshaving from 2 to 12 carbon atoms, preferably from 4 to 6 carbon atoms.

Examples of suitable alkanediols are ethylene glycol, 1,2-propanediol,1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 1,5-pentanediol,1,6-hexanediol, 2,4-dimethyl-2-ethyl-1,3-hexanediol,2,2-dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol,2-ethyl-2-isobutyl-1,3-propanediol and 2,2,4-trimethyl-1,6-hexanediol,in particular ethylene glycol, 1,3-propanediol, 1,4-butanediol or2,2-dimethyl-1,3-propanediol (neopentyl glycol); cyclopentanediol,1,4-cyclohexanediol, 1,2-cyclohexanedimethanol,1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol or2,2,4,4-tetramethyl-1,3-cyclobutanediol. Particular preference is givento 1,4-butanediol, in particular in combination with adipic acid ascomponent a1) and 1,3-propanediol, in particular in combination withsebacic acid as component a1). 1,3-propanediol has the additionaladvantage of being obtainable in the form of a renewable raw material.It is also possible to use mixtures of different alkanediols.

The ratio of component b1 (diol) to diacids A generally set in stages i)and ii) of the process is from 1.5 to 2.5 and preferably from 1.8 to2.2.

The compounds b2) preferably comprise crosslinking agents comprising atleast three functional groups. Particularly preferred compounds havefrom three to six hydroxy groups. Examples that may be mentioned are:tartaric acid, citric acid, malic acid; trimethylolpropane,trimethylolethane; pentaerythritol; polyethertriols, and glycerol,trimesic acid, trimellitic acid, trimellitic anhydride, pyromelliticacid, and pyromellitic dianhydride. Preference is given to polyols, suchas trimethylolpropane, pentaerythritol, and in particular glycerol. Thecompounds b2 can act as branching agents or else as crosslinking agents.By using components b2, it is possible to construct biodegradablepolyesters which are pseudoplastic. The rheology of the melts improves;the biodegradable polyesters are easier to process, for example easierto draw by melt-solidification processes to give foils. The compounds b2have a shear-thinning effect, and viscosity therefore decreases underload.

The amounts used of the compounds b2 are preferably from 0.01 to 2% byweight, with preference from 0.05 to 1% by weight, with particularpreference from 0.08 to 0.20% by weight, based on the amount of polymerafter stage iii).

The polyesters on which the polyester mixtures of the invention arebased can comprise further components alongside components A and B.

Suitable dihydroxy compounds c1 are diethylene glycol, triethyleneglycol, polyethylene glycol, polypropylene glycol andpolytetrahydrofuran (polyTHF), particularly preferably diethyleneglycol, triethylene glycol and polyethylene glycol, and mixtures ofthese may also be used, as may compounds which have different variablesn (see formula I), for example polyethylene glycol which comprisespropylene units (n=3), obtainable, for example, by using methods ofpolymerization known per se and polymerizing first with ethylene oxideand then with propylene oxide, and particularly preferably a polymerbased on polyethylene glycol with different variables n, where unitsformed from ethylene oxide predominate. The molar mass (M_(n)) of thepolyethylene glycol is generally selected within the range from 250 to8000 g/mol, preferably from 600 to 3000 g/mol.

According to one of the preferred embodiments for producing thesemiaromatic polyesters use may be made, for example, of from 15 to 98mol %, preferably from 60 to 99.5 mol %, of the diols B and from 0.2 to85 mol %, preferably from 0.5 to 30 mol %, of the dihydroxy compoundsc1, based on the molar amount of B and c1.

Hydroxycarboxylic acid c2) that can be used for the production ofcopolyesters is: glycolic acid, D-, L-, or D,L-lactic acid,6-hydroxyhexanoic acid, cyclic derivatives of these, such as glycolide(1,4-dioxane-2,5-dione), D- or L-dilactide(3,6-dimethyl-1,4-dioxane-2,5-dione), p-hydroxybenzoic acid, or elsetheir oligomers and polymers, such as 3-polyhydroxybutyric acid,polyhydroxyvaleric acid, polylactide (for example that obtainable in theform of NatureWorks® (Cargill)), or else a mixture of3-polyhydroxybutyric acid and polyhydroxyvaleric acid (the latter beingobtainable as Biopol® from Zeneca) and, for producing semiaromaticpolyesters, particularly preferably the low-molecular-weight and cyclicderivatives thereof.

Examples of amounts which may be used of the hydroxycarboxylic acids arefrom 0.01 to 50% by weight, preferably from 0.1 to 40% by weight, basedon the amount of A and B.

The amino-C₂-C₁₂ alkanol or amino-C₅-C₁₀ cycloalkanol used (componentc3) which for the purposes of the present invention also include4-aminomethylcyclohexane-methanol, are preferably amino-C₂-C₆ alkanols,such as 2-aminoethanol, 3-amino-propanol, 4-aminobutanol,5-aminopentanol or 6-aminohexanol, or else amino-C₅-C₆ cycloalkanols,such as aminocyclopentanol and aminocyclohexanol, or a mixture of these.

The diamino-C₁-C₈ alkanes (component c4) used are preferablydiamino-C₄-C₆ alkanes, such as 1,4-diaminobutane, 1,5-diaminopentane or1,6-diaminohexane (hexamethylenediamine, “HMD”).

In one preferred embodiment for producing the semiaromatic polyesters,use may be made of from 0.5 to 99.5 mol %, preferably from 0.5 to 50 mol%, of c3, based on the molar amount of B, and of from 0 to 50 mol %,preferably from 0 to 35 mol %, of c4, based on the molar amount of B.

The component c5 used can comprise aminocarboxylic acids selected fromthe group consisting of caprolactam, 1,6-aminocaproic acid, laurolactam,1,12-aminolauric acid, and 1,11-aminoundecanoic acid.

The amounts generally used of c5 are from 0 to 20% by weight, preferablyfrom 0.1 to 10% by weight, based on the total amount of components A andB.

The component d1 used comprises an isocyanate or a mixture of variousisocyanates. It is possible to use aromatic or aliphatic diisocyanates.However, it is also possible to use isocyanates of higher functionality.

For the purposes of the present invention, an aromatic diisocyanate d1is especially tolylene 2,4-diisocyanate, tolylene 2,6-diisocyanate,diphenylmethane 2,2′-diisocyanate, diphenylmethane 2,4′-diisocyanate,diphenylmethane 4,4′-diisocyanate, naphthylene 1,5-diisocyanate, orxylylene diisocyanate.

Among these, particular preference is given to diphenylmethane 2,2′-,2,4′-, or 4,4′-diisocyanate as component d1. The latter diisocyanatesare generally used in the form of a mixture.

An isocyanate d1 that can also be used, having three rings, istri(4-isocyanato-phenyl)methane. Polynuclear aromatic diisocyanates areproduced by way of example during production of diisocyanates having oneor two rings.

Component d1 can also comprise subordinate amounts of uretdione groups,for example up to 5% by weight, based on the total weight of componentd1, for example for capping of the isocyanate groups.

For the purposes of the present invention, an aliphatic diisocyanate d1is especially any of the linear or branched alkylene diisocyanates orcycloalkylene diisocyanates having from 2 to 20 carbon atoms, preferablyfrom 3 to 12 carbon atoms, examples being hexamethylene1,6-diisocyanate, isophorone diisocyanate, ormethylenebis(4-isocyanatocyclohexane). Particularly preferred aliphaticdiisocyanates d1 are isophorone diisocyanate and especiallyhexamethylene 1,6-diisocyanate.

Among the preferred isocyanurates are the aliphatic isocyanurates thatderive from alkylene diisocyanates or from cycloalkylene diisocyanates,where these have from 2 to 20 carbon atoms, preferably from 3 to 12carbon atoms, examples being isophorone diisocyanate ormethylenebis(4-isocyanatocyclohexane). These alkylene diisocyanates canbe either linear or branched compounds. Particular preference is givento isocyanurates based on n-hexamethylene diisocyanate, examples beingcyclic trimers, pentamers, or higher oligomers of hexamethylene1,6-diisocyanate.

The amounts generally used of component d1 are from 0.01 to 4% byweight, preferably from 0.05 to 2% by weight, particularly preferablyfrom 0.2 to 1.2% by weight, based on the amount of polymer after stageiii).

Examples of suitable di- or oligofunctional peroxides (component d2) arethe following compounds: benzoyl peroxide,1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane,1,1-bis(tert-butylperoxy)methylcyclododecane, n-butyl4,4-bis(butylperoxy)valerate, dicumyl peroxide, tert-butylperoxybenzoate, dibutyl peroxide,α,α-bis(tert-butyl-peroxy)diisopropylbenzene,2,5-dimethyl-2,5-di(tert-butylperoxy)hexane,2,5-dimethyl-2,5-di(tert-butylperoxy)hex-3-yne, andtert-butylperoxycumene.

The amount used of component d2 is from 0.01 to 4% by weight, preferablyfrom 0.1 to 2% by weight, and particularly preferably from 0.2 to 1% byweight, based on the biopolymer.

The component d3 used can comprise difunctional or oligofunctionalepoxides, such as: hydroquinone, diglycidyl ether, resorcinol diglycidylether, 1,6-hexanediol diglycidyl ether, and hydrogenated bisphenol Adiglycidyl ether. Other examples of epoxides comprise diglycidylterephthalate, diglycidyl tetrahydrophthalate, diglycidylhexahydro-phthalate, dimethyldiglycidyl phthalate, phenylene diglycidylether, ethylene diglycidyl ether, trimethylene diglycidyl ether,tetramethylene diglycidyl ether, hexamethylene diglycidyl ether,sorbitol diglycidyl ether, polyglycerol polyglycidyl ether,pentaerythritol polyglycidyl ether, diglycerol polyglycidyl ether,glycerol polyglycidyl ether, trimethylolpropane polyglycidyl ether,resorcinol diglycidyl ether, neopentyl glycol diglycidyl ether, ethyleneglycol diglycidyl ether, diethylene glycol diglycidyl ether,polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether,dipropylene glycol diglycidyl ether, polypropylene glycol diglycidylether, and polybutylene glycol diglycidyl ether.

A particularly suitable component d3a is a copolymer comprising epoxygroups and based on styrene, acrylic ester and/or methacrylic ester d3a.The units bearing epoxy groups are preferably glycidyl (meth)acrylates.Compounds that have proven advantageous are copolymers having aproportion of more than 20% by weight, particularly preferably more than30% by weight, and with particular preference more than 50% by weight,of glycidyl methacrylate in the copolymer. The epoxy equivalent weight(EEW) in these polymers is preferably from 150 to 3000 g/equivalent,particularly preferably from 200 to 500 g/equivalent. The averagemolecular weight (weight average) M_(W) of the polymers is preferablyfrom 2000 to 25 000, in particular from 3000 to 8000. The averagemolecular weight (number average) M_(n) of the polymers is preferablyfrom 400 to 6000, in particular from 1000 to 4000. The polydispersity(Q) is generally from 1.5 to 5. Copolymers of the abovementioned typecomprising epoxy groups are marketed by way of example by BASF ResinsB.V. with trademark Joncryl® ADR. Particularly suitable chain extendersare Joncryl® ADR 4368, long-chain acrylates as described in EPApplication No. 08166596.0, and Cardura® E10 from Shell.

The amount of component d3 used, based on the biopolymer, is from 0.01to 4% by weight, preferably from 0.1 to 2% by weight, and particularlypreferably from 0.2 to 1% by weight. Component d3 can also be used asacid scavenger. In this embodiment, it is preferable that theconcentration used of d3 is from 0.01 to 0.5% by weight (stage iva), andthat this is followed by chain extension using component d1, d2 and/ord3a (stage ivb), the concentration of which added is preferably from 0.2to 1.2% by weight.

The component d4 used can comprise di- or oligofunctional oxazolines,oxazines, caprolactams, and/or carbodiimides.

Bisoxazolines are generally obtainable by the process disclosed inAngew. Chem. Int. Ed., vol. 11 (1972), pp. 287-288. Particularlypreferred bisoxazolines and bisoxazines are those in which the bridgingmember is a single bond, a (CH₂)_(z)-alkylene group; where z=2, 3, or 4,e.g. methylene, ethane-1,2-diyl, propane-1,3-diyl, or propane-1,2-diyl,or a phenylene group. Particularly preferred bisoxazolines that may bementioned are 2,2′-bis(2-oxazoline), bis(2-oxazolinyl)methane,1,2-bis(2-oxazolinyl)ethane, 1,3-bis(2-oxazolinyl)propane or1,4-bis(2-oxazolinyl)butane, in particular 1,4-bis(2-oxazolinyl)benzene,1,2-bis(2-oxazolinyl)benzene or 1,3-bis(2-oxazolinyl)benzene. Furtherexamples are: 2,2′-bis(2-oxazoline), 2,2′bis(4-methyl-2-oxazoline),2,2′-bis(4,4′-dimethyl-2-oxazoline), 2,2′-bis(4-ethyl-2-oxazoline),2,2′-bis(4,4′-diethyl-2-oxazoline), 2,2′-bis(4-propyl-2-oxazoline),2,2′-bis(4-butyl-2-oxazoline), 2,2′-bis(4-hexyl-2-oxazoline),2,2′-bis(4-phenyl-2-oxazoline), 2,2′-bis(4-cyclohexyl-2-oxazoline),2,2′-bis(4-benzyl-2-oxazoline),2,2′-p-phenylenebis(4-methyl-2-oxazoline),2,2′-p-phenylenebis(4,4′dimethyl-2-oxazoline),2,2′-m-phenylenebis(4-methyl-2-oxazoline),2,2′-m-phenylenebis(4,4′-dimethyl-2-oxazoline),2,2′-hexamethylenebis(2-oxazoline), 2,2′-octamethylenebis(2-oxazoline),2,2′-decamethylenebis(2-oxazoline),2,2′-ethylenebis(4-methyl-2-oxazoline),2,2′-tetramethylenebis(4,4′-dimethyl-2-oxazoline),2,2′-9,9′-diphenoxyethanebis(2-oxazoline),2,2′-cyclohexylenebis(2-oxazoline), and2,2′-diphenylenebis(2-oxazoline).

Preferred bisoxazines are 2,2′-bis(2-oxazine), bis(2-oxazinyl)methane,1,2-bis(2-oxazinyl)ethane, 1,3-bis(2-oxazinyl)propane, or1,4-bis(2-oxazinyl)butane, in particular 1,4-bis(2-oxazinyl)benzene,1,2-bis(2-oxazinyl)benzene, or 1,3-bis(2-oxazinyl)-benzene.

Carbodiimides and polymeric carbodiimides are marketed by way of exampleby Lanxess with trademark Stabaxol® or by Elastogran with trademarkElastostab®.

Examples are: N,N′-di-2,6-diisopropylphenylcarbodiimide,N,N′-di-o-tolylcarbodiimide, N,N′-diphenylcarbodiimide,N,N′-dioctyldecylcarbodiimide, N,N′-di-2,6-dimethylphenyl-carbodiimide,N-tolyl-N′-cyclohexylcarbodiimide,N,N′-di-2,6-di-tert-butylphenyl-carbodiimide,N-tolyl-N′-phenylcarbodiimide, N,N′-di-p-nitrophenylcarbodiimide,N,N′-di-p-aminophenylcarbodiimide, N,N′-di-p-hydroxyphenylcarbodiimide,N,N′-dicyclohexyl-carbodiimide, N,N′-di-p-tolylcarbodiimide,p-phenylenebisdi-o-tolylcarbodiimide,p-phenylenebisdicyclohexylcarbodiimide,hexamethylenebisdicyclohexylcarbodiimide,4,4′-dicyclohexylmethanecarbodiimide, ethylenebisdiphenylcarbodiimide,N,N′-benzyl-carbodiimide, N-octadecyl-N′-phenylcarbodiimide,N-benzyl-N′-phenylcarbodiimide, N-octadecyl-N′-tolylcarbodiimide,N-cyclohexyl-N′-tolylcarbodiimide, N-phenyl-N′-tolylcarbodiimide,N-benzyl-N′-tolylcarbodiimide, N,N′-di-o-ethylphenylcarbodiimide,N,N′-di-p-ethylphenylcarbodiimide,N,N′-di-o-isopropylphenylcarbodiimide,N,N′-di-p-isopropylphenylcarbodiimide,N,N′-di-o-isobutylphenylcarbodiimide,N,N′-di-p-isobutylphenylcarbodiimide,N,N′-di-2,6-diethylphenylcarbodiimide,N,N′-di-2-ethyl-6-isopropylphenylcarbodiimide,N,N′-di-2-isobutyl-6-isopropylphenylcarbodiimide,N,N′-di-2,4,6-trimethylphenylcarbodiimide,N,N′-di-2,4,6-triisopropylphenylcarbodiimide,N,N′-di-2,4,6-triisobutylphenylcarbodiimide, diisopropylcarbodiimide,dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide,tert-butylisopropylcarbodiimide, di-β-naphthylcarbodiimide, anddi-tert-butylcarbodiimide.

The amount of component d4 used, based on the biopolymer, is from 0.01to 4% by weight, preferably from 0.1 to 2% by weight, and particularlypreferably from 0.2 to 1% by weight. Component d4 can also be used asacid scavenger. In this embodiment, it is preferable that theconcentration used of d4 is from 0.01 to 0.5% by weight (stage iva), andthat this is followed by chain extension using component d1, d2 and/ord3a (stage ivb), the concentration of which added is preferably from 0.2to 1.2% by weight.

In one preferred embodiment of the process of the invention, betweenstages iii) and iv), or during stage iv), a component selected from thefollowing group is added: lubricants (e1), nucleating agents (e2),and/or compatibilizers (e3). It is particularly preferable thatcomponent E is added at the end of stage iii).

Particular lubricants or mold-release agents (component e1) that haveproven successful are hydrocarbons, fatty alcohols, higher carboxylicacids, metal salts of higher carboxylic acids, e.g. calcium stearate orzinc stearate, fatty acid amides, such as erucamide, and types of wax,e.g. paraffin waxes, beeswax or montan waxes. Preferred lubricants areerucamide and/or types of wax and particularly preferably combinationsof these lubricants. Preferred types of wax are beeswaxes and esterwaxes, in particular glycerol monostearate or dimethylsiloxane, orpolydimethylsiloxane, e.g. Belsil® DM from Wacker. By adding thelubricants prior to chain extension, the lubricants can be linked tosome extent to the polymer chain. This method can provide effectivesuppression of premature exudation of the lubricants from the finishedpolymer compositions.

The amount added of component e1 is generally from 0.05 to 2.0% byweight and preferably from 0.1 to 1.0% by weight, based on the polymercomposition at the end of stage iii).

Nucleating agents (components e2) that can be used are generallyinorganic compounds, such as talc, chalk, mica, silicon oxides, orbarium sulfate. Compounds that have proven particularly successful forthe polyesters of the invention are aromatic polyesters, such aspolyethylene terephthalate and in particular polybutylene terephthalate.Surprisingly, it has been found that the nucleating agent e2 issubstantially more effective when added after stage iii) than when addedafter stage iv). The amount used of the nucleating agent can be reducedto about half for the same technical effect, e.g. rapid crystallizationand avoidance of tack. In other words, polymer compositions are obtainedwhich, although they still have very good biodegradability by virtue oftheir low content of aromatic blocks, nevertheless are non-tacky byvirtue of improved crystallization behavior.

The amount of component e2 added is generally from 0.05 to 10.0% byweight, preferably from 0.05 to 5.0% by weight, and particularlypreferably from 0.1 to 1.0% by weight, based on the polymer compositionat the end of stage iii).

Compatibilizers that have proved advantageous comprise aliphaticpolyesters, such as polylactic acid, polycaprolactone,polyhydroxyalkanoate, or polyglycolic acid (PGA). When added at the endof stage iii), they can become linked to the polymer chain to someextent. Improved compatibility of the polymer mixtures is achieved whenthe aliphatic or semiaromatic polyesters are later mixed with thesepolyesters, such as polylactic acid, polycaprolactone, orpolyhydroxyalkanoate, and it is often possible to omit use of furthercompatibilizers. If the aliphatic or semiaromatic polyesters are mixedafter chain extension with one of the abovementioned mixing partners,the polymer components have less compatibility. In those instances, itis often necessary to add a compatibilizer to the polymer mixture.

The amount added of component e3 is generally from 0.05 to 15.0% byweight, preferably from 0.1 to 8.0% by weight, and with particularpreference from 0.1 to 5.0% by weight, based on the polymer compositionat the end of stage iii).

Particular preference is given to, biodegradable semiaromatic polyesterswhich comprise, as aliphatic dicarboxylic acid (component a1)), succinicacid, adipic acid, or sebacic acid, esters thereof, or a mixture ofthese; as aromatic dicarboxylic acid (component a2)), terephthalic acidor its esters; as diol component (component B), 1,4-butanediol or1,3-propanediol, as component b2) glycerol, pentaerythritol,trimethylolpropane, and, as component d1), hexamethylene diisocyanate.

The process of the invention can also be used to produce aliphaticpolyesters. Aliphatic polyesters are polyesters made of aliphatic C₂-C₁₂alkanediols and of aliphatic C₄-C₃₆ alkanedicarboxylic acids, such aspolybutylene succinate (PBS), polybutylene adipate (PBA), polybutylenesuccinate adipate (PBSA), polybutylene succinate sebacate (PBSSe),polybutylene sebacate adipate (PBSeA), polybutylene sebacate (PBSe), orcorresponding polyesteramides. The aliphatic polyesters are marketed byShowa Highpolymers as Bionolle and by Mitsubishi as GSPla. EP08165370.1describes more recent developments.

The intrinsic viscosities to DIN 53728 of the aliphatic polyestersproduced by the process of the invention are generally from 150 to 320cm³/g and preferably from 150 to 250 cm³/g auf.

The MVR (melt volume rate) to EN ISO 1133 (190° C., 2.16 kg weight) isin general from 0.1 to 70 cm³/10 min, preferably from 0.8 to 70 cm³/10min, and in particular from 1 to 60 cm³/10 min.

The acid numbers to DIN EN 12634 are generally from 0.01 to 1.2 mgKOH/g, preferably from 0.01 to 1.0 mg KOH/g, and with particularpreference from 0.01 to 0.7 mg KOH/g.

The aliphatic and semiaromatic polyesters mentioned and the polyestermixtures of the invention are biodegradable.

For the purposes of the present invention, the feature “biodegradable”is achieved by a substance or a substance mixture if this substance orthe substance mixture exhibits, as defined in DIN EN 13432, a percentagedegree of biodegradation of at least 90%.

Biodegradation generally leads to decomposition of the polyesters orpolyester mixtures in an appropriate and demonstrable period of time.The degradation can take place by an enzymatic, hydrolytic, or oxidativeroute, and/or via exposure to electromagnetic radiation, such as UVradiation, and can mostly be brought about predominantly via exposure tomicroorganisms, such as bacteria, yeasts, fungi, and algae.Biodegradability can be quantified by way of example by mixing polyesterwith compost and storing it for a particular period. By way of example,according to DIN EN 13432, CO₂-free air is passed through ripenedcompost during the composting process, and the compost is subjected to adefined temperature profile. The biodegradability here is defined as apercentage degree of biodegradation by way of the ratio of the netamount of CO₂ released from the specimen (after subtraction of theamount of CO₂ released by the compost without specimen) to the maximumamount of CO₂ that can be released from the specimen (calculated fromthe carbon content of the specimen). Biodegradable polyesters orbiodegradable polyester mixtures generally exhibit marked signs ofdegradation after just a few days of composting, examples being fungalgrowth, cracking, and perforation.

Other methods for determining biodegradability are described by way ofexample in ASTM D5338 and ASTM D6400.

The semiaromatic polyesters are generally random copolyesters, i.e. thearomatic and aliphatic diacid units are incorporated entirely randomly.The distribution of the lengths of the individual blocks can becalculated by the method of B. Vollmert, Grundriss der makromolekularenChemie [Basic principles of macromolecular chemistry]. As described byWitt et al. in J. Environ. Pol. Degradation, volume 4, No. 1 (1996),page 9, degradation of aromatic model oligomers where n z 3 in compostis normally very slow. However, in the case of semiaromatic polyesters,block structures are rapidly degraded.

The molar mass (Mn) of the preferred semiaromatic polyesters isgenerally in the range from 1000 to 100 000 g/mol, in particular in therange from 9000 to 75 000 g/mol, preferably in the range from 20 000 to50 000 g/mol, and their molar mass (Mw) is generally from 50 000 to 300000 g/mol, preferably from 75 000 to 200 000 g/mol, and their Mw/Mnratio is generally from 1 to 6, preferably from 2 to 4. The meltingpoint is in the range from 60 to 170° C., preferably in the range from80 to 150° C.

The MVR (melt volume rate) to EN ISO 1133 (190° C., 2.16 kg weight)after stage 4 is generally from 0.5 to 6.0 cm³/10 min, preferably from1.0 to 5.0 cm³/10 min, and particularly preferably from 1.5 to 3 cm³/10min.

The intrinsic viscosities of the biodegradable aliphatic/aromaticpolyesters to DIN 53728 are generally high and from 160 to 250 cm³/g,preferably from 170 to 220 cm³/g. The dimension for the intrinsicviscosities below is always cm³/g.

It is desirable to provide aliphatic/aromatic copolyesters which notonly have high intrinsic viscosity but also have low acid number to DINEN 12634. The lower the acid number of the aliphatic/aromaticcopolyesters, the greater the hydrolysis resistance of the polyesters,either alone or in a mixture with biopolymers such as starch(thermoplastified or not plastified), polylactide (PLA),polyhydroxyalkanoates, aliphatic polyester such as Bionolle®, cellulose,or polycaprolactone. The shelf life of the polyesters or polyestermixtures improves accordingly.

It is moreover easier to chain-extend the prepolyesters obtainable instage iii), where these have a small acid number to DIN EN 12634-<1.2 mgKOH/g, preferably <1.0 mg KOH/g, particularly preferably <0.9 mg KOH/g.The result is short residence times with more effective molar massincrease and little increase in acid number in the following stage iv).It is possible to achieve almost complete avoidance of side reactions,or undesired formation of fish eyes. There is a preferred possibilityfor still further lowering the acid number if the prepolyesters obtainedin stage iii) are treated in an intermediate step iva) with acidscavengers, such as d3 and/or d4, and only then subjected to chainextension ivb).

Overall, the biodegradable copolyesters of the invention(chain-extended—see claim 13) with a small acid number and low MVR havethe following advantages:

-   -   less molecular weight decrease during processing, such as for        example compounding with starch    -   better storage stability    -   better melt stability during production of foils, and    -   because of high molecular weight, excellent performance        characteristics in injection molding and in particular during        extrusion.

The process of the invention is described in more detail below.

Components A, B, and, if appropriate, C are mixed in a preliminarystage. The materials generally mixed are 1.0 mol equivalent of a mixturecomposed of aliphatic and aromatic dicarboxylic acids or their ester(component A), from 1.1 to 1.5 mol equivalents, preferably from 1.2 to1.4 mol equivalents, of aliphatic dihydroxy compounds (component b1),

and from 0 to 2% by weight, preferably from 0.01 to 0.5% by weight,based on the amount of polymer after stage iii), of a compound b2; ifappropriate, further comonomers (component C) are also premixed.

In one preferred procedure, the dicarboxylic acids are used in the formof free acids (component A). The mixture here is mixed in theabovementioned mixing ratios—without addition of any catalyst—to give apaste, the temperature of which is usually controlled to from 20 to 70°C.

As an alternative to this, the liquid esters of the dicarboxylic acids(component A) are mixed with the dihydroxy compound and, if appropriate,further comonomers, in the abovementioned mixing ratios—without additionof any catalyst—generally at a temperature of from 140 to 200° C.

In a further alternative, one or both dicarboxylic acids is/areesterified in a preliminary stage with the aliphatic dihydroxy compoundsto give a purely aliphatic or aromatic polyester, and this is then mixedwith the respective other dicarboxylic acid and further aliphaticdihydroxy compound, and also, if appropriate, compound b2. By way ofexample, polybutylene terephthalate and/or polybutylene adipate can beused in this preliminary stage.

In stage i), the (preliminary-stage) liquid, slurry, and/or pastedescribed above, composed of aliphatic and aromatic dicarboxylic acids(A) and of an aliphatic dihydroxy compound (b1), if appropriate compound(b2), and of further comonomers (component C) is esterified in thepresence of from 0.001 to 1% by weight, preferably from 0.03 to 0.2% byweight, based on the amount of polymer after stage iii, of a catalyst,as far as an intrinsic viscosity which is generally from 5 to 15 cm³/gto DIN 53728.

The excess diol component is generally removed by distillation, andafter, for example, distillative purification, returned to the circuit.

In stage i), either the entire amount or a portion—preferably from 50 to80 parts—of the catalyst is metered in. The catalysts used usuallycomprise zinc compounds, aluminum, and, in particular, titaniumcompounds. Another advantage of titanium catalysts, such as tetrabutylorthotitanate or tetra(isopropyl)orthotitanate, when compared with thetin compounds, antimony compounds, cobalt compounds, and lead compoundsoften used in the literature, e.g. tin dioctanoate, is that residualamounts remaining within the product of the catalyst or downstreamproducts of the catalyst are less toxic. This circumstance isparticularly important in the biodegradable polyesters, since they passdirectly into the environment, for example in the form of compostingbags or mulch foils.

Simultaneously, in stage i), a temperature of from 180 to 260° C. andpreferably from 220 to 250° C., and also a pressure of from 0.6 to 1.2bar and preferably from 0.8 to 1.1 bar are set. Stage i) can be carriedout in a mixing assembly, such as a hydrocyclone. Typical residencetimes are from 1 to 2 hours.

Stage i) and ii) are advantageously carried out in a single reactor,such as a tower reactor (see, for example, WO 03/042278 and DE-A 199 29790), the reactor having the internals appropriate for each stage.

Further component b1, and also the optional component c), can be added,if appropriate, in stage i) and/or ii). The ratio of component B (diol)to diacids A set in stage i) is generally from 1.5 to 2.5 and preferablyfrom 1.8 to 2.2.

In stage ii), the liquid obtained in stage i (esterification) is fed,together with, if appropriate, the residual amount of catalyst, into areactor appropriate for the precondensation reaction. Reactors whichhave proven suitable for the precondensation reaction are a tube-bundlereactor, a reactor cascade, or a bubble column, and in particular adownflow cascade, if appropriate with degassing unit (procedure iia).The reaction temperatures set are generally from 230 to 270° C.,preferably from 240 to 260° C., and the pressures set at the start ofstage ii) are generally from 0.1 to 0.5 bar, preferably from 0.2 to 0.4bar, and the pressures set at the end of stage ii) are generally from 5to 100 mbar, preferably from 5 to 20 mbar. Using residence times of from60 to 160 minutes, it is possible to produce aliphatic/aromaticprepolyesters whose intrinsic viscosity is from 20 to 60 cm³/g,preferably from 25 to 55 cm³/g, to DIN 53728. The acid numbers to DIN EN12634 of the prepolyesters can still vary greatly after stage ii) as afunction of the production method. If the preliminary stage starts fromthe free dicarboxylic acids, the acid numbers at the end of stage ii)are still relatively high; however they then fall in stage iii). If thepreliminary stage starts from the corresponding dicarboxylic esters, theacid number at the end of stage ii) is comparatively small. However, inthis case the acid numbers increase during the course of stage iii). Theacid numbers to DIN EN 12634 at the end of stage ii) are generally from0.7 to 2 mg KOH/g.

The tower reactors described in detail in WO-A 03/042278 and WO-A05/042615 have proved particularly advantageous for the precondensationreaction ii), in which the product stream is passed cocurrently througha single- or multistage falling-film evaporator, where the reactionvapors—in particular water, THF, and, if dicarboxylic esters are used,alcohols—are drawn off at a plurality of sites distributed over thereactor (procedure iib). The cocurrent procedure described in WO-A03/042278 and WO-A 05/042615, with continuous removal of the reactionvapors—at least at a plurality of sites—is expressly incorporated hereinby way of reference. This procedure in particular has the followingadvantages:

-   -   pumps for conveying of the product stream can substantially be        omitted; a simpler gravimetric-flow method can be used for the        progress of the product; the reactor can be run at slightly        superatmospheric pressure, or atmospheric pressure, or using        slightly subatmospheric pressure (see above),    -   in a procedure which is in any case very non-aggressive, the        continuous removal of the reaction vapors in situ from the        reaction mixture shifts the equilibrium to the side of the        reaction products; the rapid removal of the reaction vapors        moreover avoids, or at least suppresses, side-reactions;    -   using the procedure described above, it is generally possible to        produce aliphatic/aromatic prepolyesters whose intrinsic        viscosity is from 25 to 55 cm³/g to DIN 53728; these        prepolyesters moreover have very low acid numbers to DIN EN        12634.

The reaction vapors, which consisted essentially of water and, ifdicarboxylic esters are used, of alcohol, or—if the diol 1,4-butanediolis used—of excess diol and THF by-product, are purified by conventionaldistillation processes and returned to the process.

In the polycondensation step iii), a deactivator for the catalyst isadmixed, if appropriate, with the precondensed polyester. Deactivatorsthat can in particular be used are phosphorus compounds: eitherorganophosphites such as phosphonous acid or phosphorous acid. It isparticularly advisable to use deactivators if high-reactivity titaniumcatalysts are used. The amounts that can be added of the deactivatorsare from 0.001 to 0.1% by weight, preferably from 0.01 to 0.05% byweight, based on the amount of polymer after stage iii). The Ti/P ratiopreferably set is from 1.3-1.5:1 and particularly preferably from1.1-1.3:1.

If appropriate, a color stabilizer for the condensation process isadmixed with the precondensed polyester in the polycondensation stepiii). Color stabilizers that can be used are in particular phosphoruscompounds. Examples are phosphoric acid, phosphorous acid, triphenylphosphite, triphenyl phosphate, IrgafosPEPQ, sodium hypophosphite andsodium phosphite. These phosphorus compounds can also be used in theform of a mixture. The use of color stabilizers generally leads to areduction in condensation rate. Triphenyl phosphate is a particularlysuitable color stabilizer, since there is no adverse effect oncondensation rate.

An amount that can be added of the color stabilizers is from 0.001 to1.5% by weight, preferably from 0.01 to 1.0% by weight, based on theamount of polymer after stage iii). It is preferable to set a Ti/P ratio(mol/mol) of from 1.0:0.3 to 1.0 and with particular preference from1.0:0.5 to 1.0.

In the polycondensation step iii), an activator for the condensationprocess is, if appropriate, admixed with the precondensed polyester.Activators that can be used are in particular phosphorus compounds.Examples are disodium hydrogenphosphate, calcium hypophosphite, calciumphosphite, calcium phosphate, sodium hypophosphite, sodium phosphite,triphenyl phosphite, triphenyl phosphate, trimethyl phosphate, triethylphosphate, tripropyl phosphate, tributyl phosphate, Irgafos 168. Thesephosphorus compounds can also be used in the form of a mixture.Particularly suitable activators are disodium hydrogenphosphate andsodium phosphite. An amount that can be added of the activators is from0.001 to 1.5% by weight, preferably from 0.01 to 1.0% by weight, basedon the amount of polymer after stage iii). It is preferable to set aTi/P ratio (mol/mol) of from 1.0 to 1.5:1, and with particularpreference from 1.1 to 1.3:1.

Combined use of color stabilizer and activator is of particularinterest, an example being triphenyl phosphate/disodiumhydrogenphosphate.

The polycondensation process takes place in what is known as a finisher.Finishers that have proven particularly suitable are reactors such as arotating-disk reactor or a cage reactor, these being as described inU.S. Pat. No. 5,779,986 and EP 719582. The latter reactor, inparticular, takes account of the fact that the viscosity of thepolyester increase with increasing reaction time. Reaction temperaturesset are generally from 220 to 270° C., preferably from 230 to 250° C.,and pressures set are generally from 0.2 to 5 mbar, preferably from 0.5to 3 mbar. Using residence times of from 30 to 90 minutes, preferablyfrom 40 to 80 minutes, it is possible to produce aliphatic/aromaticpolyesters with intrinsic viscosity to DIN 53728 of from 70 to 130cm³/g, and acid numbers to DIN EN 12634 of from 0.5 to 1.2 mg KOH/g,preferably from 0.6 to 0.9 mg KOH/g. Typical molecular weights (Mn) arefrom 10 000 to 25 000, with molecular weights (Mw) of from 35 000 to 70000 at this stage.

In the chain-extension process (stage iv), the polycondensed polyesteris fed into an extruder, or into a continuous kneader (List reactor), orinto a static mixer, together with from 0.01 to 4% by weight, preferablyfrom 0.1 to 2% by weight, and with particular preference from 0.5 to1.2% by weight, based on the polyester. The following internals may bementioned by way of example: the static mixer can use SMR, SMX, or SMXLelements, or a combination of these, e.g. from Sulzer Chemtech AG,Switzerland. Examples of a List reactor, as a function of applicationsector, are: a single-shaft DISCOTHERM B or twin-shaft CRP or ORPreactors. Extruders that can be used are single- or twin-screwextruders.

Chain extenders that can be used are the isocyanates or isocyanuratesd1, peroxides d2, and epoxides d3a described above. By way of example,these are diisocyanates selected from the group consisting of tolylene2,4-diisocyanate, tolylene 2,6-diisocyanate, diphenylmethane 4,4′- and2,4′-diisocyanate, naphthylene 1,5-diisocyanate, xylylene diisocyanate,hexamethylene diisocyanate, pentamethylene diisocyanate, isophoronediisocyanate, and methylenebis(4-isocyanatocyclohexane). Particularpreference is given to hexamethylene diisocyanate.

For production of polyesters within the claimed viscosity range whichsimultaneously have low acid numbers, it can be advantageous to add whatare known as acid scavengers, for example components d3 and d4 describedin the introduction. The concentration used here is preferably from 0.01to 2.0% by weight, and in particular from 0.02 to 1.0% by weight, basedon the polymer mixture. It is advisable to add the acid scavengers atthe start of, during, or at the end of stage iii), or in an upstreamstep iva) prior to the chain-extension process ivb). Particularlysuitable chain extenders are components d1, d2, and d3a. However, it isalso possible to add the acid scavengers d3 and d4 after addition of thechain extenders d1 and d2.

The chain extension reaction (polyaddition, stage iv) takes place atreaction temperatures of from 220 to 270° C., preferably from 230 to250° C., and at superatmospheric pressure or atmospheric pressure, as afunction of the system used. Using residence times of from 2 to 30minutes, preferably from 4 to 15 minutes, it is possible to producealiphatic/aromatic polyesters whose intrinsic viscosity is from 160 to250 cm³/g to DIN 53728 and whose acid numbers to DIN EN 12634 arepreferably from 0.5 to 1.2 mg KOH/g and particularly preferably from 0.6to 1.0 mg KOH/g.

MVR (melt volume rate) to EN ISO 1133 (190° C., weight 2.16 kg) afterstage 4 is generally from 0.5 to 6.0 cm³/10 min, preferably from 1.0 to5.0 cm³/10 min, and particularly preferably from 1.5 to 3 cm³/10 min.

While the compounds b2 act as described above in particular ascrosslinking agents, the isocyanates act at low temperatures inparticular as linear chain extenders. If the chain extension reaction(stage iv) is carried out at relatively high temperatures, in particularat temperatures above 120° C., allophanate formation occurs. The chainextender then also acts as branching agent and has direct influence onthe pseudoplasticity of the biodegradable polyesters. The rheology ofthe melts improves; the biodegradable polyesters are easier to process,for example giving better results when drawn by melt-solidificationprocesses to give foils. The isocyanates d1 have a shear-thinningeffect, and this means that viscosity decreases under load.

The reactor in which the chain reaction is carried out has the internalsdescribed above, these providing good mixing of the product stream.

Because of the marked viscosity increase during the chain extensionreaction, it can be advantageous to run the chain extension reaction inthe reactor only until the chain extender has at least reacted fullywith a functional unit. The chain length increase can be completed byway of example in a separate stirred vessel or in a tube withoutinternals. This method can avoid blockages and wall deposits.

The fully reacted melt is generally transferred directly by way of amelt filter to the finishing process, for example underwaterpelletization.

Aliphatic/aromatic polyesters, can be produced with good processabilityand efficiency using the four-stage process of the invention.

If the precondensation reaction ii) is, for example, carried out in atower reactor, where the product stream is passed cocurrently through afalling-film evaporator, and the reaction vapors are removed in situfrom the reaction mixture, it is possible to obtain prepolyesters whoseintrinsic viscosities are from 25 to 55 cm³/g to DIN 53728 and whoseacid numbers are simultaneously low: smaller than 0.9 mg KOH/g. If freeacids are used—for example terephthalic acid—the acid number in stageii) can remain relatively high, but in stage iii) it falls to below 0.9mg KOH/g. These prepolyesters can give more efficient and lessaggressive polycondensation, and, particularly using hexamethylenediisocyanate, they can give more efficient and less aggressive chainextension. Using this embodiment of the process of the invention it ispossible for the first time to produce aliphatic/aromatic polyesterswhose intrinsic viscosity is greater than 160 cm³/g to DIN 53728 andwhose acid number is smaller than 1 mg KOH/g, and whose MVR to ENISO1133 is smaller than 6.0 cm³/10 min.

The polyesters of the invention (see claims 16 and 19) have excellentprocessability, because their MVR is low. They also have a very low acidnumber, and this in turn results in good hydrolysis resistance. Thepolyesters of the invention are therefore also suitable for theproduction of biodegradable polymer mixtures comprising one or morecomponents selected from the group consisting of aliphatic polyester,such as Bionolle® (Showa Highpolymer), polycaprolactone, starch(thermoplastified or non-plastified), cellulose, polyhydroxyalkanoates(products of PHB Industrial, Tianan, Metabolix), and polylactic acid,such as NatureWorks® (Cargill).

These biodegradable polyester mixtures generally comprise

-   i) from 5 to 95% by weight, preferably from 20 to 80% by weight, of    the polyester of the invention;-   ii) from 95 to 5% by weight, preferably from 80 to 20% by weight, of    at least one or more components selected from the group consisting    of aliphatic polyester, polycaprolactone, starch, cellulose,    polyhydroxyalkanoate, and polylactic acid.

In contrast, the aliphatic/aromatic polyesters known from the prior arthave the following properties:

Acid number Intrinsic viscosity MVR [mg KOH/g] [cm³/g] [cm³/10 min] DIN12634 DIN 53728 ISO 1133 EaststarBio ® 3 — 28 (PBAT) EnPol ®G8060 6.3174 9 (PBAT) PBAT = Polybutylene adipate-co-terephthalateTest Methods:

The acid number was determined to DIN EN 12634 of October 1998. Thesolvent mixture used comprised a mixture of 1 part by volume of DMSO, 8parts by volume of propan-2-ol, and 7 parts by volume of toluene. Thespecimen was heated to 50° C., and the circuit used a single-rodelectrode and potassium chloride filling. The standard solution used wastetramethylammonium hydroxide.

Intrinsic viscosity was determined to DIN 53728, part 3, Jan. 3, 1985.The solvent used comprised the following mixture:phenol/dichlorobenzene, 50/50 ratio by weight.

Melt volume flow rate (MVR) was determined to ISO 1133. The testconditions were 190° C., 2.16 kg. The melting time was 4 minutes. TheMVR gives the rate of extrusion of a molten plastics molding compositionthrough an extrusion die of defined length and defined diameter underthe prescribed conditions: temperature, load, and position of piston.The volume in the barrel of an extrusion plastometer extruded in adefined time is determined.

EXAMPLES 1. Continuous Production of PolybutyleneAdipate-Co-Terephthalate with HDI (Process According to claims 1 to 4)

To produce the biodegradable polyester, 440 kg/h of dimethylterephthalate, 510 kg/h of a prepolyester composed of adipic acid and1,4-butanediol (Mn 2000 g/mol), 270 kg/h of 1,4-butanediol, and 1.0 kg/hof glycerol were added continuously with 0.55 kg/h of tetrabutylorthotitanate to a multistage stirred-tank cascade. The reaction mixturewas transesterified at atmospheric pressure within the stirred-tankcascade at temperatures of from 180° C. to 210° C. and with a residencetime of 2.5 h, and the resulting condensation product methanol wasremoved by distillation. The intrinsic viscosity (IV) of the resultantlow-molecular-weight polyester was 10 cm³/g.

The reaction mixture was then heated to 260° C. in a downstreamriser-tube reactor, in which the melt is passed (see DE 19509551)through a large number of heated tubes with addition of 0.30 kg/h oftetrabutyl orthotitanate, the pressure is lowered to 100 mbar, and mostof the excess butanediol is removed by distillation. After a residencetime of 45 minutes, the IV of the polyester was 23 cm³/g.

After addition of 0.28 kg/h of phosphorous acid, the reaction mixturewas transferred to a rotating-disk reactor (cf. U.S. Pat. No. 5,779,986)and polycondensed at a temperature of 250° C. and at a pressure of 4mbar for a further 45 minutes, and the remaining excess of butanediolwas removed by distillation. The IV of the resultant polyester was 89cm³/g and its acid number (AN) was 1.0 mg KOH/g.

After the polycondensation reaction, 8.0 kg/h of hexamethylenediisocyanate (HDI) were metered into the polyester at 240° C., using astatic mixing system. After a residence time of 7 minutes, the polyesterwas pelletized, using an underwater pelletizer, and dried. The IV of theresultant polyester was 191 cm³/g, its molar mass Mn was 36 000 g/mol(and Mw was respectively 125 000 g/mol), its MVR was 3 cm³/10 min, andits AN was 1.1 mg KOH/g. A List reactor was used in a further experimentin stage iv) instead of a static mixer. The polymers thus obtained hadcomparable properties (acid number, intrinsic viscosity, MVR).

2. Continuous Production of Polybutylene Adipate-Co-TerephthalateChain-Extended Using HDI (Process According to claims 5 and 6)

To produce the biodegradable polyester, 19 kg/h of terephthalic acid, 19kg/h of adipic acid, 32 kg/h of 1,4-butanediol, and 0.05 kg/h ofglycerol were mixed physically at 35° C., and then the mixture wascontinuously transferred to an esterification reactor (e.g. designed inthe form of a hydrocyclone as described by way of example in WO03/042278 A1). The mixture was esterified at a temperature of 240° C.,with a residence time of 1.5 h, and at a pressure of 0.85 bar, withaddition of a further 16 kg/h of 1,4-butanediol and 0.022 kg/h oftetrabutyl orthotitanate (TBOT), and the resulting condensation productwater was removed by distillation, as also was some of the excess ofbutanediol. The intrinsic viscosity (IV) of the resultantlow-molecular-weight polyester was 12 cm³/g.

The reaction mixture was then passed through a downflow cascade (asdescribed by way of example in WO 03/042278 A1) at a temperature risingfrom 250 to 260° C., with a residence time of 2 h, and at a pressurefalling from 300 mbar to 10 mbar, with addition of a further 0.012 kg ofTBOT/h, and most of the excess butanediol was removed by distillation.The intrinsic viscosity (IV) of the resultant polyester was 47 cm³/g.

After addition of 0.01 kg/h of phosphorous acid, the reaction mixturewas transferred to a polycondensation reactor (as described by way ofexample in EP 0719582), and polycondensed at a temperature of 245° C.and at a pressure of 1 mbar for a further 45 minutes, and the remainingexcess of butanediol was removed by distillation. The IV of theresultant polyester was 95 cm³/g and its acid number (AN) was 0.6 mgKOH/g. After the polycondensation reaction, 0.4 kg/h of hexamethylenediisocyanate (HDI) were metered into the polyester at 240° C., using astatic mixing system. After a residence time of 7 minutes, the polyesterwas pelletized, using an underwater pelletizer, and dried. The IV of theresultant polyester was 235 cm³/g, its molar mass Mn was 47 000 g/mol(and Mw was respectively 165 000 g/mol), its MVR was 1.9 cm³/10 min, andits AN was 0.7 mg KOH/g. A List reactor was used in a further experimentin stage iv) instead of a static mixer. The polymers thus obtained hadcomparable properties (acid number, intrinsic viscosity, MVR).

3. Comparative Example of Batchwise Production of PolybutyleneAdipate-Co-Terephthalate Chain-Extended Using HDI

To produce the biodegradable polyester, 3700 kg of dimethylterephthalate, 4300 kg of a prepolyester composed of adipic acid and1,4-butanediol (Mn 2000 g/mol), 2200 kg of 1,4-butanediol, 8.5 kg ofglycerol, and 2.4 kg of tetrabutyl orthotitanate were added to a stirredtank. The reaction mixture was heated in stages within a period of 8 hto a temperature of 245° C., and at the same time the pressure waslowered in stages to 5 mbar, while the excess of 1,4-butanediol wasremoved by distillation. Subsequently, 0.6 kg of phosphorous acid werethen added, with stirring, in vacuo. The intrinsic viscosity (IV) of theresultant polyester was 91 cm³/g and its acid number (AN) was 1.3 mgKOH/g. After the polycondensation reaction, 6.8 kg/h of hexamethylenediisocyanate (HDI) were metered into the polyester at 240° C., using astatic mixing system. After a residence time of 7 minutes, the polyesterwas pelletized, using an underwater pelletizer, and dried. The IV of theresultant polyester was 170 cm³/g, its molar mass Mn was 32 000 g/mol(and Mw was 95 000 g/mol), its MVR was 6.0 cm³/10 min, and its AN was1.5 mg KOH/g.

The invention claimed is:
 1. A biodegradable polyester based onaliphatic and aromatic dicarboxylic acids and on aliphatic dihydroxycompounds, obtained by a continuous process, the process comprisingmixing the aliphatic dihydroxy compounds, the aliphatic and aromaticdicarboxylic acids, and, optionally, further comonomers (component C) ismixed, without addition of a catalyst, to give a paste, or, as analternative, the liquid esters of the dicarboxylic acids are fed intothe system, as also are the dihydroxy compound and, optionally, furthercomonomers, without addition of any catalyst, where i) in a first stage,this mixture, together with the entire amount or with a portion of thecatalyst, is continuously esterified or, respectively, transesterified;ii) in a second stage, the transesterification or, respectively,esterification product obtained in i) is continuously precondensed to anintrinsic viscosity of from 20 to 70 cm³/g to DIN 53728; iii) in a thirdstage, the product obtainable from ii) is continuously polycondensed toan intrinsic viscosity of from 60 to 170 cm³/g to DIN 53728, and iv) ina fourth stage, the product obtainable from iii) is reacted continuouslywith a chain extender D in a polyaddition reaction to an intrinsicviscosity of from 150 to 320 cm³/g to DIN 53728; where stage ii) iscarried out in a tower reactor, and the product stream is conductedconcurrently by way of a falling-film cascade, and the reaction vaporsare removed in situ from the reaction mixture; and where, in stage ii),the transesterification product or esterification product isprecondensed to an intrinsic viscosity of from 25 to 55 cm³/g to DIN53728.
 2. The biodegradable polyester based on aliphatic and aromaticdicarboxylic acids and on aliphatic dihydroxy compounds according toclaim 1, where stage iv) is carried out in an extruder, List reactor, orstatic mixer and where, in stage iv), hexamethylene diisocyanate(component d1) is used as chain extender.
 3. The biodegradable polyesterbased on aliphatic and aromatic dicarboxylic acids and on aliphaticdihydroxy compounds according to claim 1, where, after stage iii), from0.05 j to 5.0% by weight, based on the polymer composition after stageiii, of a nucleating agent e2 is added.
 4. The biodegradable polyesterbased on aliphatic and aromatic dicarboxylic acids and on aliphaticdihydroxy compounds according to claim 1, wherein, after stage iii),from 0.05 to 15.0% by weight, based on the polymer composition afterstage iii, of a compatibilizer e3 is added.
 5. A biodegradable polyestercomposed of: A) an acid component made of a1) from 35 to 60 mol % of atleast one aliphatic dicarboxylic acid or ester thereof, or a mixturethereof, selected from the group consisting of: succinic acid, adipicacid, and sebacic acid; a2) from 65 to 40 mol % of terephthalic acid orester thereof, or a mixture thereof, where the molar percentages ofcomponents a1) and a2) give a total of 100%, and; B) a diol component(b1) selected from the group consisting of: 1,4-butanediol or1,3-propanediol, or a mixture thereof; b2) from 0.05 to 1% by weight,based on components A and B, of glycerol, D) a component d1) from 0.1 to2% by weight, based on components A and B, of hexamethylenediisocyanate; and with an acid number, measured to DIN EN 12634, whichis smaller than 1.0 mg KOH/g, and with an MVR to ISO 1133 which issmaller than 6 cm³/10 min (190° C., 2.16 kg weight); wherein thebiodegradable polyester is obtained by a continuous process, the processcomprising mixing the aliphatic dihydroxy compounds, the aliphatic andaromatic dicarboxylic acids, and, optionally, further comonomers(component C), without addition of a catalyst, to give a paste, or, asan alternative, the liquid esters of the dicarboxylic acids are fed intothe system, as also are the dihydroxy compound and, optionally, furthercomonomers, without addition of any catalyst, where i) in a first stage,this mixture, together with the entire amount or with a portion of thecatalyst, is continuously esterified or, respectively, transesterified;ii) in a second stage, the transesterification or, respectively,esterification product obtained in i) is continuously precondensed to anintrinsic viscosity of from 20 to 70 cm³/g to DIN 53728; iii) in a thirdstage, the product obtainable from ii) is continuously polycondensed toan intrinsic viscosity of from 60 to 170 cm³/g to DIN 53728, and iv) ina fourth stage, the product obtainable from iii) is reacted continuouslywith a chain extender D in a polyaddition reaction to an intrinsicviscosity of from 150 to 320 cm³/g to DIN 53728; where stage ii) iscarried out in a tower reactor, and the product stream is conductedconcurrently by way of a falling-film cascade, and the reaction vaporsare removed in situ from the reaction mixture; and where, in stage ii),the transesterification product or esterification product isprecondensed to an intrinsic viscosity of from 25 to 55 cm³/g to DIN53728.
 6. A biodegradable polyester mixture comprising i) from 5 to 95%by weight of a polyester according to claim 5; ii) from 95 to 5% byweight of at least one or more components selected from the groupconsisting of aliphatic polyester, polycaprolactone, starch, cellulose,polyhydroxyalkanoate, polyglycolic acid, and polylactic acid.
 7. Thebiodegradable polyester according to claim 1, where the biodegradablepolyester is composed of: A) an acid component composed of a1) from 30to 99 mol % of at least one aliphatic dicarboxylic acid or its esters,or a mixture thereof, a2) from 1 to 70 mol % of at least one aromaticdicarboxylic acid or its esters, or a mixture thereof, and a3) from 0 to5 mol % of a compound comprising sulfonate groups, where the total ofthe molar percentages of components a1) to a3) is 100%, and B) a diolcomponent composed of: b1) at least equimolar amounts with respect tocomponent A of a C₂-C₁₂ alkanediol, or a mixture thereof, and b2) from 0to 2% by weight, based on components A and b1), of a compound comprisingat least 3 functional groups; and, optionally, one or more componentsselected from C) a component selected from c1) at least one dihydroxycompound comprising ether functions and having the formula IHO—[(CH₂)_(n)—O]_(m)—H  (I) where n is 2, 3 or 4 and m is a whole numberfrom 2 to 250, c2) at least one hydroxycarboxylic acid of the formulaIIa or IIb

where p is a whole number from 1 to 1500 and r is a whole number from 1to 4, and G is a radical selected from the group consisting ofphenylene, —(CH₂)_(q)—, where q is a whole number from 1 to 5, —C(R)H—and —C(R)HCH₂, where R is methyl or ethyl, c3) at least one amino-C₂-C₁₂alkanol, or at least one amino-C₅-C₁₀ cycloalkanol, or a mixture ofthese, c4) at least one diamino-C₁-C₈ alkane, c5) at least oneaminocarboxylic acid compound selected from the group consisting ofcaprolactam, 1,6-aminocaproic acid, laurolactam, 1,12-aminolauric acid,and 1,11-aminoundecanoic acid, or mixtures composed of c1) bis c5), andD) from 0.01 to 4% by weight, based on the amount of polyester afterstage iii, of at least one component selected from the group d1) to d4)d1) of a di- or oligofunctional isoscyanate and/or isocyanurate, d2) ofa di- or oligofunctional peroxide, d3) of a di- or oligofunctionalepoxide, d4) of a di- or oligofunctional oxazoline, oxazine,caprolactam, and/or carbodiimide; E) from 0 to 10% by weight, based onthe amount of polyester after stage iii of a component selected from thegroup e1) to e3) e1) of a lubricant, e2) of a nucleating agent, e3) ofan aliphatic polyester selected from the group consisting of: polylacticacid, polycaprolactone, polyhydroxyalkanoate.
 8. The biodegradablepolyester according to claim 7, wherein the lubricant is erucamide or astearate.
 9. The biodegradable polyester according to claim 7, whereinthe nucleating agent is calcium carbonate, polyethylene terephthalate,or polybutylene terephthalate.
 10. The biodegradable polyester accordingto claim 1, where the biodegradable polyester comprises, as aliphaticdicarboxylic acid (component a1)), succinic acid, adipic acid, orsebacic acid, esters thereof, or a mixture of these; as aromaticdicarboxylic acid (component a2)), terephthalic acid or its esters; asdiol component (component B), 1,4-butanediol or 1,3-propanediol, ascomponent b2) glycerol, pentaerythritol, trimethylolpropane, and, ascomponent d1), hexamethylene diisocyanate.
 11. The biodegradablepolyester according to claim 1, where theesterification/transesterification (stage i)) uses a hydrocyclone withattached heat exchange, and stage i), ii), and iii) is carried out inthe presence of a titanium catalyst.
 12. The biodegradable polyesteraccording to claim 1, where stage ii) is carried out in a tower reactor,and the product stream is conducted concurrently by way of afalling-film cascade, and the reaction vapors are removed in situ fromthe reaction mixture.
 13. The biodegradable polyester according to claim12, where, in stage ii), the transesterification product oresterification product is precondensed to an intrinsic viscosity of from25 to 55 cm³/g to DIN
 53728. 14. The biodegradable polyester accordingto claim 1, where, between stage ii) and iii), from 0.001 to 0.1% byweight of a deactivating phosphorus compound, or from 0.001 to 1.5% byweight of a color-stabilizing or activating phosphorus compound, isadded to the product stream.
 15. The biodegradable polyester accordingto claim 1, where, at the start of, during, or at the end of stage iii,or in an upstream step iva of the chain-extension process ivb, from 0.01to 2.0% by weight, based on the respective polymer composition, of anacid scavenger selected from the group of a di- or oligofunctionalepoxide (d3), oxazoline, oxazine, caprolactam, and/or carbodiimide (d4)is added.
 16. The biodegradable polyester according to claim 1, wherestage iii) is carried out in a rotating-disk reactor or cage reactor.17. The biodegradable polyester according to claim 1, where, after stageiii), from 0.05 to 2.0% by weight, based on the polymer compositionafter stage iii, of a lubricant e1 is added.
 18. The biodegradablepolyester according to claim 1, where stage iv) is carried out in anextruder, List reactor, or static mixer.
 19. The biodegradable polyesteraccording to claim 18, where, in stage iv), hexamethylene diisocyanate(component d1) is used as chain extender.